Method of sulfochlorinating hydrocarbons



3,007,911 Patented Nov. 7, 1961 fice 3,007,911 METHOD OFSULFOCHLORINATING HYDRDCARBONS Helen Sellei Beretvas, Chicago, andRobert S. Barnes,

Jr., Olympia Fields, Ill, assignors to Standard Oil Company, Chicago,Ill., a corporation of Indiana No Drawing. Filed Dec. 2, 1958, Ser. No.777,605

I 21 Claims. (Cl. 260139) This invention relates to improvements in thesulfochlorination of unsaturated hydrocarbons. In particular, it relatesto the treatment of unsaturated hydrocarbons with sulfur chloride toproduce compositions having high sulfur content, high chlorine content,unusually light color, and high temperature color stability.

Sulfurization of unsaturated hydrocarbons has been effected in the pastby processes which generally comprise the steps of suifurization byreacting unsaturated hydrocarbons with sulfur chloride in the presenceof added Water at a temperature from about 80 F. to about 150 F.,neutralization of the resulting product with an alkaline reagent such asan alkali metal or alkaline earth oxide, hydroxide or carbonate, andseparation of the neutralization product from the hydrocarbon insolubleproducts by filtration. The products for such a process usually have ahigh sulfur content and a high chlorine content. It has now been foundthat high sulfur-high chlorine-containing hydrocarbon compositions canbe obtained in a process which eliminates the time consumingneutralization step and allows completion of the process reac tionswithin a minimum amount of time and without necessitating the handlingof strong alkali materials. Furthermore, it has been found that by ourpresent process hydrocarbons of unusually high sulfur content, lightcolor and having excellent high temperature color stability, may beproduced.

Therefore, an object of the present invention is to producesulfochlorinated hydrocarbons having light color and excellent colorstability at relatively high temperatures.

Another object of the present invention is to provide a process forsulfochlorinating unsaturated hydrocarbons which permits the eliminationof time consuming neutralization steps.

A further object is to produce improved materials which may be employedas additives to cutting oils and gear oils and as intermediates for thepreparation of additives for use in internal combustion motor oils,diesel oils, etc., and which impart extreme pressure characteristics tothe oils in which they are used. Other objects and advantages will beapparent from the following.

Broadly stated, the present invention comprises the steps ofsulfochlorinating a linearly unsaturated hydrocarbon by treatment withsulfur chloride, refluxing the sulfochlorinated hydrocarbon in thepresence of a solvent and water mixture, and finishing the resultingrefluxed material by removing undesirable and occluded matter. Thelinearly unsaturated hydrocarbons which may be sulfochlorinated inaccordance with this invention are those unsaturated hydrocarbons havingat least one double bond in a linear chain and are intended to includeolefins, aromatics having unsaturated alkyl groups, cycloparalfms havingunsaturated alkyl groups, partially unsaturated polymers, unsaturatedacids, alcohols and esters,

etc. The olefins used in the present invention are those having from 6to 18 carbon atoms and preferably from 7 to 12 carbon atoms. Synthololefins prepared by Fischer Tropsch synthesis of carbon monoxide andhydrogen may also be used but it is advantageous to purify the rawsynthol olefins by fractional percolation through Attapulgus clay,silica, alumina, etc., before sulfochlorination to get a product havingless objectionable odor. The partially unsaturated polymers are thosehaving linear unsaturation, such as partially unsaturated polymersprepared from acyclic olefins, monoolefins, aromatics having unsaturatedalkyl groups and the like.

In carrying out the sulfochlorination in accordance with the presentinvention, an unsaturated hydrocarbon or a mixture of unsaturatedhydrocarbons is treated with sulfur chloride. It has been foundadvantageous to carry the sulfur chloride treatment out in the presenceof water to obtain a lighter colored product although water is notnecessary to the sulfochlorination reaction. The sulfur chloride usedmay be any of the usual sulfur chlorides, such as sulfur monochloride,sulfur dichloride, or mixtures thereof. Because of its higher sulfurcontent, sulfur monochloride is preferred. In sulfochlorinating theunsaturated hydrocarbon in the presence of water We prefer toincrementally add the sulfur chloride and water simultaneously butseparately to the unsaturated hydrocarbon. However, we have found thatthere are other acceptable procedures in conducting the reaction. Thesulfochlorination may be carried out by incrementally adding the sulfurchloride to a mixture of the unsaturated hydrocarbon and water. In thiscase the sulfur chloride should be added slowly to keep the reactionfrom becoming too vigorous and so as not to exceed the boiling point ofthe mixture. Another method of sulfochlorination within the scope of thepresent invention is by adding the unsaturated hydrocarbons to a mixtureof sulfur chloride and water. In this case special precaution must betaken to provide adequate cooling because the reaction is particularlyvigorous. Following still another procedure, the water may be added to amixture of sulfur chloride and unsaturated hydrocarbon, however, thisprocedure produces a product of darker color than that obtained by theother above mentioned technique and is therefore the least preferredprocedure. If water is omitted, the sulfur chloride should be addedslowly to the hydrocarbon. In. any of the above procedures, agitating ormixing is advantageous to minimize localized vigorous reactions.

In accordance with the preferred sulfochlorination procedure, sulfurchloride and Water are added simultaneously but separately to theunsaturated hydrocarbon, the sulfur chloride being added in molaramounts. In the present invention We use from about 0.3 to about 2.0moles of sulfur chloride and if the unsaturated hydrocarbons are olefinspreferably from about 0.4 to 0.8 mole of sulfur chloride per mole ofunsaturated hydrocarbon. In the sulfochlorination reaction suflicientsulfur chloride is used to provide approximately 0.4 to 34.0 atoms ofsulfur per unsaturated olefinic bond in the reacting hydrocarbon. Whenpolymers are reacted generally more than 60% of the unsaturated polymerwill react. Greater molar amounts of sulfur chloride per mole ofhydrocarbon should be used with polymers having a large number ofunsaturated bonds and Where more highly unsaturated olefins, such asdiolefins, are used. Because the reaction is vigorous if allowed toproceed uninhibited from a total mixture of all reactants used, thesulfur chloride is added at a rate slow enough to maintain theexothermic reaction within a temperature range of about C. to about 90C. and preferably not exceeding 55 C. It is also advantageous to coolthe separate reactants before combining them or to cool the reactionitself in order to maintain the reaction within the above temperaturerange. Allowing the temperature to exceed 90 C. will cause discolorationof the product and will also cause the reactants to flow from the top ofthe reactor where an open reactor is used. Even temperatures in excessof 55 C. may cause discoloration. The water is added separately duringthe sulfochlorination over a period of from about 10 to 45 minutes. Weuse from 1 to about 50 volume percent, preferably from about to about 26volume percent, of added water based on the unsaturated hydrocarbon. Theaddition of water is advantageous in that it improves the colorstability of the sulfochlorinated prod uct. The water also helps attaina more complete reaction. The sulfochlorination reaction is allowed tocontinue until complete, and the refluxing step is started immediatelyafter the reaction is complete, i.e., immediately after the completionof reactant addition. Because the reaction is exothermic in nature, itis preferred to apply external cooling to the reaction mixture while thereaction proceeds. By applying external cooling, the period of timerequired for the reaction may be greatly decreased because removal ofexothermic heat will allow faster addition of the reactants to theunsaturated hydrocarbon without producing problems of productdiscoloration. Following the preferred procedure as outlined above thesulfur chloride treatment may be completed within about one hour andshould not take longer than about five or six hours.

During sulfochlorina-tion it may become desirable to add an antifoamagent such as a silicone polymer or other suitable material to inhibitexcessive turbulence and foaming of the reaction mixture.

Phosphorus sulfide such as P S P 5 P S etc. may be advantageouslyincorporated in small amounts into the reactants of the presentinvention to further increase the color stability of the reactionproducts. The phosphorus sulfide apparently reacts with the unsaturatedhydrocarbon during sulfochlorination and during the later reflux steps.We prefer to add the phosphorus sulfide during the sulfochlorina-tionstep before the addition of sulfur chloride because we have found thataddition at this time produces a sulfochlorinated hydrocarbon of greatercolor stability. When phosphorus sulfide is added to the reactants,water may also be added to aid the reaction and further increase colorstability. In carrying out the preferred procedure, we mix phosphorussulfide with the unsaturated hydrocarbon prior to the addition of sulfurchloride. The amount of phosphorus sulfide added is in the range of fromabout .0025 mole to about 0.2 mole and preferably from about .005 toabout .05 mole per mole of unsaturated hydrocarbon. Thus, the amount byweight of phosphorus sulfide used is dependent upon the molecular weightof the hydrocarbon. Accordingly, for example, we have found thatsufficient phosphorus sulfide to give a product having 0.1 to 2.5 weightpercent phosphorus based upon the weight of an unsaturated hydrocarbonhaving seven carbon atoms is used during sulfochlorination. When thephosphorus sulfide is added to the sulfochlorination reaction, it is advantageous to carry the reaction out in the presence of a nitrogenatmosphere to prevent flashes which may normally be caused by thephosphorus compound in the presence of air. It has been found that whenphosphorus sulfide is added during the sulfochlorination step thereactants are more stable at higher temperatures and discolorationproblems arising from uncontrolled temperatures in the reaction aresubstantially minimized.

Upon completion of the sulfochlorination of the olefin as set out above,the reaction product is refluxed, preferably immediately aftersulfochlorination, at least once in the presence of a solvent and watermixture. Although the reaction product may be first removed from theunreacted components and impurities as by filtration or other knownseparating methods, we prefer to add the solvent and water mixturedirectly to the reaction mixture at the completion ofsu-lfochlorination.

In the reflux step, total reflux of the mixture of reactants is effectedso that all of the reactants as well as substantially all of the solventand water are retained in the mixture with no appreciable amount of thereaction mixture being driven off with the exception of HCl. We use awater cooled refluxing condenser in the reflux step. The reflux iscarried out at the total reflux temperature of the reaction mixture,which temperature normally will not exceed about 100 C. underatmospheric conditions, because of the presence of the water. Thesolvents which are useab-le in the solvent and water mixture are theoxygen-containing essentially non-reacting watermiscible organiccompounds boiling below 100 C. and preferably above 50 C. The solventmay advantageously be a water-miscible ketone or alcohol. Thewatermiscible alcohols are preferred as solvents and of particularpreference is isopropanol. Lower temperatures may be advantageously useddown to about 65 C., at atmospheric pressure, such as when methanol isused as the solvent or even to about 5560 C. as when acetone is used asthe solvent. We prefer to reflux the reactants in the range of fromabout 75 C. to about 95 C. in the presence of a mixture of water andisopropanol, the solvent of particular preference. Of course, the aboverecited temperatures correspond to refluxing at substantiallyatmospheric pressure; changes in pressure may require changes in thetemperature range and such changes are to be considered within the scopeof the present invention. The reflux is continued for a sufficientperiod of time to eliminate labile chlorine as HCl. The period of timefor refluxing is in the range of from about 10 minutes to about tenhours and preferably from about one-half hour to about four hours.During reflux, the loose chlorine from sulfochlorination is eliminatedas HCl substantially dissolved in the water layer removed afterrefluxing. Reflux may be repeated one or more times and we have foundthat two refluxes of about one hour each are suflicient. When reflux isrepeated, the water layer is separated from the reactants after refluxand a second reflux mixture of solvent and water is added to thereactants, preferably immediately. The total time of reflux when morethan one reflux is used should fall within the above limits.

In the first refluxing, we prefer to use a mixture of about 50% solventand about 50% water by volume and if a second or subsequent refluxing isused, we prefer to use a mixture of about water and about 20% solvent byvolume; however, any solvent and water mixture is suitable. The amountsof the mixture used may vary with the hydrocarbon starting material aswell as the number of refluxes. For example, it has been found that 500cc. of isopropanol and water mixture per 1000 grams of an olefinstarting material is sufficient for the first refluxing and 250 cc. per1000" grams is suflicient if subsequent refluxing is desired.

Refluxing with solvent and water eliminates the labile chlorine andother unreacted inorganic impurities left in the product from the sulfurchloride treatment step. The labile chlorine is eliminated in the formof hydrogen chloride and the severity, length and number of refluxes ispartially determined by the amount of chlorine which needs to beeliminated from the product. The reflux also serves to increase thesulfur content of the product. If phosphorus sulfide is used duringSlllfOChlOl'lHflJtlOH, the phosphorus content of the product is alsoincreased in comparison with a sodium hydroxide neutralized product,

supra. The increase of phosphorus and sulfur content can be readilyunderstood by reference to the following comparison of analyses ofproducts prepared in accordance with the present invention with thoseprepared by a process using neutralization of a sulfur chloride treatedproduct with sodium hydroxide after eliminating unreacted olefins byblowing with nitrogen.

1 All products above before reflux or N aOH neutralization as indicatedwere prepared by suliochlorinating a C olefin with 70 gm. 01 per 100 gm.C1 olefin in the presence of H 0.

2 Isopropanol used as the solvent.

3 Percent PiSa based on weight of unsaturated hydrocarbon.

As is indicated by the above analyses, the refluxed products fromsulfochlon'nation of an olefin having seven carbon atoms were found tohave a sulfur content in the general range of 28 to 31% based on totalweight and a higher phosphorus content than was obtained with a sodiumhydroxide neutralized product which has been prepared using an equalamount of phosphorus sulfide and which has not been refluxed. Thephosphorus and sulfur content of the isopropanol-water refluxed productsis considerably higher than that of NaOH neutralized products preparedfrom the same relative amounts of phosphorus and sulfur withoutisopropano-Lwater refluxing.

Another characteristic of the products formed by our process is highchlorine content. This property is most important from the standpoint ofuse of the products in cutting oils. Although labile chlorine issubstantially removed from the products by the reflux step, combinedchlorine in the products is present in unusually large quantities forcompositions which also have such a high sulfur content. The light colorof the products from our process, unusual in high chlorine and sulfurcontaining compositions, is another advantage in their use particularlyin cutting oils.

A single reflux for from about one-half to three hours is usuallysuflicient to eliminate the bulk of unreacted inorganic ingredients.However, two washings in the reflux are more adequate and are preferredand three or more washings may be used.

After refluxing has been completed, the aqueous layer from the refluxstep is separated from the refluxed product. The refluxed product may beblown with air or an inert gas or may be air evaporated to remove lowmolecular weight unreacted hydrocarbons and other impurities and nofiltering of the product is necessary. Small amounts of water in theproduct may be removed with a drying agent. When blowing with an inertgas we prefer to use nitrogen although any such inert gas may beconveniently employed. The length of time required for removal of theolefins by blowing with air or an inert gas will depend upon the amountof air or inert gas used, the amount of product to be blown and theamount of unreacted olefins and other impurities present in the product.Air evaporation may take as long as 144 hours to remove impurities fromthe product. However, this period can be substantially lessened bypartially finishing the product by blowing with inert gas before airevaporation. When high molecular weight hydrocarbons, such as polymers,are used, blowing and evaporation is not absolutely necessary becausetraces of water may be eliminated with a drying agent.

As illustrations only and not intended to be limitations upon the scopeof this invention, the following are offered as examples of the practiceof this invention.

Example A 15 00 g. of C olefin prepared by the polymerization ofpropylene with butylenes were reacted with 1050 g. (.52 mole per mole ofC olefin) of S Cl in the presence of .150 g. of water and 150 g. (.045mole per mole of C olefin) of P 8 in a nitrogen atmosphere. The reactionwas started at a temperature of 4 C. and was allowed to proceed at atemperature no higher than 42 C. for four hours and thirty-five minutes.The resulting sulfochlorinated product was refluxed in the presence of750 ccs. of a mixture of 50% water and 50% isopropanol at a temperatureranging from C. to C. for a period of two hours. The aqueous phase wasremoved from the reactants and 375 ccs. of a mixture of 80% water and20% isopropanol were immediately added. The reactants were subjected toa second reflux at approximately the same temperatures as the firstreflux for a period of one hour. The aqueous phase was removed from theproduct and the product was blown with N for 8 hours and left exposed toair for 89 hours to allow the unreacted olefin to evaporate. The finalyield of product was 1912 gm. or 127%.

Example B 1,000 g. of a C olefin prepared by the polymerization ofpropylene with butylenes were reacted with 700 g. (.52 mole per mole ofC olefin) of S CI in the presence of g. of water and 100 g. .045 moleper mole of C olefin) of P 5 The reaction was started at a temperatureof 10 C. and was allowed to proceed at a temperature no higher than 24C. for 2 hours and twenty-five minutes. The resulting sulfochlorinatedproduct was refluxed in the presence of 500 ccs. of a mixture of 50%water and 50% isopropanol at a temperature ranging from 80 C. to 90 C.for a period of two hours. The aqueous phase was removed from thereactants and 250 ccs. of a mixture of 80% water and 20% isopropanolwere immediately added. The reactants were subjected to a second refluxat approximately the same temperatures for a period of one hour. Theaqueous phase was emoved from the product and the product was blown withair to remove unreacted olefin. A final yield of 1333 g. or 133% wasobtained.

Example C 1000 g. of C olefin prepared by the polymerization ofpropylene with butylenes were reacted with 700 g. (.52 mole per mole ofC olefin) of S Cl in the presence of 100 g. of water and 50 g. (.023mole per mole of C7 olefin) of P 8 in a nitrogen atmosphere. Thereaction was started at a temperature of 10 C. and was allowed toproceed at a temperature no higher than 33 C. for two hours and fifteenminutes. The resulting sulfo-chlorinated product was refluxed in thepresence of 500 ccs. of a mixture of 50% water and 50% isopropanol at atemperature ranging from 80 C. to 90 C. for a period of two hours. Theaqueous phase was removed from the reactants and 250 ccs. of a mixtureof 80% water and 20% isopropanol were immediately added. The re actantswere subjected to a second reflux at approxi mately the sametemperatures as the first reflux for a period of one hour. The aqueousphase was removed from the product and the product was blown withnitrogen for 24 hours and left exposed to air for 16 hours to allow theunreacted olefin to evaporate. The final yield of product was 1229 g. or123%.

Example D 1000 g. of a C olefin prepared by the polymerization ofpropylene with butylenes were reacted with 700 g. (.52 mole per mole ofC olefin) of S Cl in the presence of 100 g. of water and 50 g. (.023mole per mole of C olefin) of P S in a nitrogen atmosphere. The reactionwas started at a temperature of C. and was allowed to proceed at atemperature no higher than 32 C. for 2 hours and fifteen minutes. Theresulting sulfochlorinated product was refluxed in the presence of 500ccs. of a mixture of 50% water and 50% isopropanol at a temperatureranging from 80 C. to 90 C. for a period of two hours. The aqueous phasewas removed from the reactants and 250 ccs. of a mixture of 80% waterand 20% isopropanol were immediately added. The reactants were subjectedto a second reflux at approximately the same temperatures for a periodof one hour. The aqueous phase was removed from the product and theproduct was blown with nitrogen for 24 hours and left exposed to air for16 hours to allow the unreacted olefins to evaporate. The final yield of1196 g. or 120% was obtained.

Example E 1000 g. of C olefin prepared by the polymerization ofpropylene with butylenes were reacted with 700 g. (.52 mole per mole ofC olefin) of S Cl in the presence of 100 g. of water and 50 g. (.023mole per mole of C olefin) of P 8 in a nitrogen atmosphere. The reactionwas started at a temperature of C. and was allowed to proceed at atemperature no higher than 26 C. for 2 hours and thirty minutes. Theresulting sulfochlorinated product was refluxed in the presence of 500ccs. of a mixture of 50% water and 50% acetone at a temperature rangingfrom 60 C. to 70 C. for a period of two hours. The aqueous phase wasremoved from the reactants and 250 ccs. of a mixture of 80% water andacetone were immediately added. The reactants were subjected to a secondreflux at approximately the same temperatures as the first reflux for aperiod of one hour. The aqueous phase was removed from the product andthe product was blown with nitrogen for 14 hours to remove unreactedolefin. The final yield of product was 1148 g. or 115%.

Example F 1000 g. of a C olefin prepared by the polymerization ofpropylene with butylenes were reacted with 700 g. (.52 mole per mole ofC olefin) of S C1 in the presence of 100 g. of water and 50 g. (.023mole per mole of C olefin) of P 3 in a nitrogen atmosphere. The reactionwas started at a temperature of 10 C. and was allowed to proceed at atemperature no higher than 33 C. for 2 hours and twenty-seven minutes.The resulting sulfochlorinated product was refluxed in the presence of500 ccs. of a mixture of 50% water and 50% isopropanol at a temperatureranging from 80 C. to 90 C. for a period of two hours. The aqueous phasewas removed from the reactants and 250 cos. of a mixture of 80% waterand 20% isopropanol were immediately added. The reactants were subjectedto a second reflux at approximately the same temperatures for a periodof one hour. The aqueous phase was removed from the product and theproduct was exposed to air for 64 hours to allow the unreacted olefin toevaporate. A final yield of 1243 g. or 124% was obtained.

Example G 1000 g. of C olefin prepared by the polymerization ofpropylene with butylenes were reacted with 700 g. (.52 mole per mole ofC olefin) of S Cl in the presence of 100 g. of water and 50 g. (.023mole per mole of C olefin) of P S in a nitrogen atmosphere. The reactionwas started at a temperature of 4 C. and was allowed to proceed at atemperature no higher than 34 C. for two hours and twenty-five minutes.The resulting sulfochlorinated product was refluxed in the presence of500 ccs. of a mixture of 50% water and 50% isopropanol at a temperatureranging from 80 C. to 90 C. for a period of two hours. The aqueous phasewas removed from the reactants and 250 ccs. of a mixture of water and20% isopropanol were immediately added. The reactants were subjected toa second reflux at approximately the same temperatures as the firstreflux for a period of 30 minutes. The aqueous phase was removed and 250ccs. of the 80% water and 20% iso propanol mixture were added and athird reflux was conducted under about the same conditions for 30minutes. The aqueous phase was removed from the product and the productwas blown with nitrogen for 13 hours to remove unreacted olefin. Thefinal yield of product was 1157 g. or 116%.

Example H 1500 g. of a C olefin prepared by the polymerization ofpropylene with butylenes were reacted with 1050 g. (.52 mole per mole ofC olefin) of S Cl in the presence of 150 g. of water and 75 g. (.023mole per mole of C olefin) of P S in a nitrogen atmosphere. The reactionwas started at a temperature of 3 C. and was allowed to proceed at atemperature no higher than 64 C. for 4 hours and twenty-five minutes.The resulting sulfochlorinated product was refluxed in the presence of750 ccs. of a mixture of 50% water and 50% isopropanol at a temperatureranging from 80 C. to C. for a period of one hour. The aqueous phase wasremoved from the reactants and 375 ccs. of a mixture of 80% Water and20% isopropanol were immediately added. The reactants were subjected toa second reflux at a temperature ranging from 80 C. to 90 C. for aperiod of one hour. The aqueous phase was removed from the product andthe product was exposed to air for 144 hours to allow unreacted olefinto evaporate. A final yield of 1627 g. or 108% was obtained.

Example I 1500 g. of C propylene tetrarner prepared by thepolymerization of propylene were reacted with 630 g. .52 mole per moleof C tetr-amer) of S Cl in the presence of g. of water and 75 g. (.038mole per mole of C tetrarner) of P 8 in a nitrogen atmosphere. Theresulting sulfochlorinated product was refluxed in the presence of 750ccs. of a mixture of 50% water and 50% isopropanol at a temperatureranging from 80 C. to 90 C. for a period of one hour. The aqueous phasewas removed from the reactants and 375 cos. of a mixture of 80% waterand 20% isopropanol were immediately added. The reactants were subjectedto a second reflux at a temperature ranging from 80 C. to 90 C. for aperiod of one hour. The aqueous phase was removed from the product andthe product was blown with nitrogen to pa tially remove unreactedolefin. The final product weighed 1851 g. or 123% yield, and containedsome unreacted olefins.

Example I 1500 g. of a C olefin prepared by the polymerization ofpropylene wit-h butylenes were reacted with 1050 g. (.52 mole per moleof C olefin) of S Cl in the presence of 150 g. of water and 15 g. (.0045mole per mole of C olefin) of P S in a nitrogen atmosphere. The reactionwas started at a temperature of 3 and was allowed to proceed at atemperature no higher than 35 C. for 4 hours and thirty-five minutes.The resulting sulfochlorinated product was refluxed in the presence of750 ccs. of a mixture of 50% water and 50% isopropanol at a temperatureranging from 80 C. to 90 C. for a period of one hour. The aqueous phasewas removed from the reactants and 375 cc. of a mixture of 80% water and20% isopropanol were immediately added. The reactants were subjected toa second reflux at approximately the same temperatures for a period ofone hour. The aqueous phase was removed from the product and the productwas blown with nitrogen for 10 hours and exposed to air for 16 hours toallow evaporation of unreacted olefin. A final yield of 1836 g. of 122%was obtained.

from the reaction vessel.

Example K 1000 g. of C olefin prepared by the polymerization ofpropylene with butylenes were reacted with 700 g. (.52 mole per mole ofC olefin) of S Cl in the presence of 100 g. of water. The reaction wasstarted at a temperature of 10 C. and was allowed to proceed at atemperature no higher than 22 C. for one hour and forty-five minutes.The resulting sulfochlorinated product was refluxed in the presence of500 cos. of a mixture of 50% water and 50% isopropanol at a temperatureranging from 80 C. to 90 C. for a period of two hours. The aqueous phasewas removed from the reactants and 250 ccs. of a mixture of 80% waterand 20% isopropanol were immediately added. The reactants were subjectedto a second reflux at approximately the same temperatures as the firstreflux for a period of one hour. The aqueous phase was removed from theproduct and the product was blown with air for 20 hours to removeunreacted olefin. The final yield of product was 1162 g. or 116%.

Example L 1500 g. of a C propylene tetramer prepared by thepolymerization of propylene were reacted with 630 g. (.52 mole per moleof C tetramer) of S Cl in the presence of 150 g. of water and 15 g.(.0076 mole per mole of C tetramer) of P C in a nitrogen atmosphere. Thereaction was started and was allowed to proceed violently as a runawayreaction with reactants spilling The resulting sulfochlorinated productwas refluxed in the presence of 750 ccs. of a mixture of 50% water and 50% isopropanol at a temperature ranging from 80 C. to 90 C. for a periodof one hour. The aqueous phase was removed from the reactants and 375ccs. of a mixture of 80% water and 20% isopro-panol were immediatelyadded. The reactants were subjected toa second reflux at approximatelythe same temperatures for a period of one hour. The aqueous phase wasremoved from the product and the product was blown with nitrogen toremove unreacted olefin. Final yield could not be determined because ofspilling over of reactants during the sulfochlorination step.

Example M 1000 g. of C olefin prepared by the polymerization ofpropylene with bu-tylenes were reacted with 700 g. (.52 mole per mole ofC olefin) of S CI The reaction was started at a temperature of C. andwas allowed to proceed at a temperature no higher than 45 C. for 2 hoursand twenty-three minutes. The resulting sulfochlorinated product wasrefluxed in the presence of 500 ccs. of a mixture of 50% water and 50%isopropanol at a temperature ranging from 80 C. to 90 C. for a period oftwo hours. The aqueous phase was removed from the reactants and 250 cos.of a mixture of 80% water and 20% isopropanol were immediately added.The reactants were subjected to a second reflux at approximately thesame temperatures as the first reflux for a period of one hour. Theaqueous phase was removed from the product and an interim sample of 200g. was taken out. The remainder of the product was blown with air for 24hours to remove unreacted olefin. The final yield of the remainder ofproduct was 1031 g.

Example N 500 g. of a partially linearly unsaturated polymer having amolecular weight of about 750 were reacted with 70 g. (.78 mole per moleof polymer) of S Cl in the presence of 25 g. (.17 mole per mole ofpolymer) of RS in a nitrogen atmosphere. The reaction was started at atemperature of 32 C. and was allowed to proceed at a temperature nohigher than 73 C. for 2 hours and fifty minutes. The resultingsulfochlorinated product was refluxed in the presence of 250 ccs. of amixture of 50% water and 50% isopropanol at a temperature ranging from80 C. to 90 C. for a period of one hour. The

aqueous phase was drained from the product and a 200 g. aliquot wastaken and dried on a steam bath. The remainder of the product wasdissolved in a solvent, filtered through paper to free it frominorganic-containing solids and after evaporation of the solvent, theremainder of the product was mixed with the dried aliquot. The finaltotal yield was 520 g. or 104%.

Example 0 500 g. of a partially linearly unsaturated polymer having amolecular weight of about 750 in the presence of 500 ccs. of a naphthadiluent to cut the viscosity of the polymer were reacted with 70 g. (.78mole per mole of polymer) of S Cl in the presence of 25 g. (.17 mole permole of polymer) of P 8 in a nitrogen atmosphere. The reaction wasstarted at a temperature of 31 C. and was allowed to proceed at atemperature not exceeding 77 C. for a period of 2 hours and fiftyminutes; The resulting sulfochlorinated product was refluxed in thepresence of 250 ccs. of a mixture of 50% water and 50% isopropanol at atemperature ranging from 61 C. to 77 C. for a period of one hour. Thereflux in this example, as in the above examples, was carried out attotal reflux temperature and the lower total reflux temperature in thisexample is attributable to the presence of the naphtha. The aqueousphase was removed from the reactants and 125 ccs. of a mixture of 80%water and 20% alcohol were immediately added. Total reflux was: repeatedfor one hour and the aqueous phase was separated from the product. Theproduct was blown with nitrogen to remove occluded naphtha but unreactedpolymer was not removed. The final product was recovered by filteringover a Buchner funnel, removing water by drying with anhydrous Na SO inthe presence of benzene and evaporating on a steam bath to remove theadded volatiles. In the multiple step product recovery, some product waslost; however 468 g. of product were recovered.

In all of the above examples, a silicone polymer antifoam agent was usedto prevent excessive foaming during sulfochlorination.

The products from the above examples were analyzed for sulfur content,chlorine content, phosphorus content and NPA color. The results aregiven in Table II.

TABLE II PRODUCT ANALYSIS Sulfur, Chlorine, Phospho- NPA Product Wt.rus, Wt. Color Percent Percent Percent Example A 29. 4 7. 52 1. 32 3Example B 25. 4 9. 5 1.03 1V -2 Example C 28. 2 8. 54 1.00 1V2-2 ExampleD 20.0 3. 56 0.91 1%2 Example E 28.0 11.48 0. 24 1V-2 Example F 27. 4 9.06 1.00 1%-2 Example G. 29. 2 7. 66 0.82 24% Example I-I 30. 6 7. 98 0.61 33% Example I 15.1 3.1 0.77 4 Example J 24. 2 11.3 0.12 4 1% ExampleK 25. 8 10. 6 0. 00 4%5 Example L 19.0 4.1 0.15 1 6 Example M. 25.8 11.00.00 7 Example N 2 4. 1 0. 5 O. 40 44% Example 0 2. 74 0.13 0. 54 44% 1In 5% blend or refined parallin distillate having a viscosity of 80 toSSU at 100 2 Contains unreacted polymer.

Table II demonstrates the high sulfur and high chlorine content andlight color of the products of the present invention. The sulfur andchlorine in the compositions formed by the present process arechemically bonded in the product and the sulfur is not physicallysuspended as in the usual high sulfur content compositions, although itis to be considered within the scope of the present invention to suspendor dissolve additional quantities of sulfur or chlorine additive in thecomposition prepared by the present process.

Further, compositions prepared in accordance with our invention possesshigh sulfur activity even when used in gear oil and cutting oilconcentrations. Accordingly, the sulfur activity of various additives,prepared by treating a C olefin with sulfur chloride in the presence ofwater and phosphorus sulfide and refluxing the product in the presenceof an isopropanol-Water mixture, was determined in blends of 2% byweight of the additive in an SAE 50 grade mineral oil. The procedureused in determining sulfur activity was that described by me in a paperwhich I presented at the 1958 meeting of the American Society ofLubricating Engineers, in Cleveland, Ohio, and published in LubricationEngineering, volume 14, No. 10, pp. 435 to 438 (1958). Briefly theprocedure used is as follows: weighed clean copper strips were immersedin 15 g. of the 2% blends in test tubes for 16 hours at temperatures of200 F., 250 F. and 300 F.; the copper strips were removed, washed withhexane and acetone and immersed for 3 minutes in a 10% potassium cyanidesolution which selectively dissolves the reaction products on the stripwithout appreciably attacking the underlying copper strip itself; thestrips were then weighed to determine the mg. weight loss as a measureof the sulfur activity. The results are compared in Table III with theresults of the same sulfur activity test conducted with the SAE 50 grademineral blending oil alone and with a 5% blend of sperm oil containingto 13% sulfur.

TABLE III Treatment During Sulioehlorination Sulfur Activity of 2% Per-Blends in Oil Mg. cent Copper Loss in 16 hrs. Gm. used for 100 gm. Phos.at F.

01 Olefin Reflnxed in Alcohol/ Prod.

H20 H20 P235 P483 200 250 300 10 1 10 None Yes- 1. 20 20 220 332 10 None2 5 Yes 0.80 22 226 292 10 2 2 None Yes, 0.20 35 156 212 10 3 1 NoneYes... 0.12 68 185 233 5% Sperm Oil Sulfur Content: 10l3%) 1.5 3. 5 32Mineral Blending Oil (No added Sulfur) 1.0 2.0 2. 5

1 .045 moles. 2 .023 moles. 3 .012 moles.

The data in Table III demonstrates the high sulfur activity of thecompositions prepared in accordance with our invention under conditionsof use at low temperatures, such as for use in gear oils.

The use of the solvent-water reflux step in accordance with the presentinvention vastly improved the color stability of the product andadditional improvement in color stability was found to accompany thepresence of a phosphorus compound in the product. Reaction productsprepared in accordance with the present invention using a C7 olefin asthe unsaturated hydrocarbons were submitted to a temperature of 130 F.for a period of 26 days and the true color changes of the products arecompared with products of other processes as indicated in Table IVbelow.

The data in Table IV demonstrate the increased product color stabilityobtainable from the use of our present invention. The C olefin,sulfochlorinated in the presence of phosphorus pentasulfide andalcohol-water refluxed, exhibits excellent color stability when aged for26 days at 130 F., equivalent to aging for approximately one year atroom temperatures. When the product was sodium hydroxide neutralized butnot refluxed, the true color was substantially increased after aging,thereby demonstrating inferior color stability. When phosphoruspentasulfide and water was eliminated separately from the compositions,the color stability also decreased somewhat. When both phosphoruspentasulfide and water were eliminated, another substantial decrease incolor stability occurred.

Concerning the refluxed compositions, as set out in Table IV, it isimportant to note that even the refluxed product (No. II) having a verylow phosphorus content (0.12%) exhibited excellent color stability onaging.

Compositions prepared from C olefins by the present process andsubmitted to temperatures of 130 F. for 26 days were then cut back to a3% blend with a refined paraflin distillate having a viscosity of 8-0 toSSU at F. to simulate practical cutting oil concentrations. The 3%blends were found to have unusually light color, generally in the NPAcolor range of from 2 to 3 /2.

The sulfochlorinated hydrocarbons produced by the present invention areparticularly useful in cutting oils where high sulfur and chlorineactivity, light color, and color stability are of great importance Thesulfochlorinated products may also be used as additives for automotivegear oils where it is desirable to incorporate sulfur compositions topass shock load tests and are applicable to many other situations Withinthe skill of the art.

An important advantage of the present process is the production of highsulfur, chlorine containing hydrocarbons having light color and suitablefor commercial use. Another advantage is the reduction in the amount oftime necessary for producing a finished sulfochlorinated composition.Other advantages will appear evident to one skilled in the art from theabove disclosures and descriptions. While we have described in detailthe preferred embodiment of the present invention, it will be apparentto those skilled in the art that certain modifications thereto arepossible so that it is understood that the pres ent invention is notintended to be limited to the details set forth above, but includeswithin its scope such modifications as come within the scope of theappended claims.

We claim:

1. In a process for the sulfochlorination of linearly unsaturatedhydrocarbons the steps comprising reacting a linearly unsaturatedhydrocarbon with a sulfur chloride and refluxing the resultingsulfochlorinated hydrocarbon in the presence of substantial portions ofa mixture of water and an oxygen-containing essentially non-reactingwater-miscible organic compound wherein the water and oxygen-containingcompound in said mixture are each TABLE IV Treatment During ProductAfter After Exposure at Sulfochlorination Preparation F. for

No. NaOH Refluxed Neutralized Per- N PA True 13 days 26 days-- 1120 1 P8 2 Isoprocent P Color Color True True pawl/H O Color Color .045 1. 20 312 100 132 0045 0. 12 44% 33 264 380 045 0. 05 4% 46 460 992 .045 0. 054V -5 60 528 1, 214 None None 44% 33 528 1, 156 None None 1- 1% 33 1, 1,856

l Grams per 100 grams C1 olefin. 2 Moles per mole of C1 olefin 13present in substantial percents at the total refluxing temperature, saidoxygen-containing compound boiling below about 100 C.

2. The process of claim 1 wherein the oxygen-containing essentiallynon-reacting water-miscible organic compound boils within the range of50 to 100 C.

3. The process of claim 1 wherein the oxygen-containing essentiallynon-reacting water-miscible organic compound is a water-misciblealcohol.

4. The process of claim 1 wherein the oxygen-containing essentiallynon-reacting water-miscible organic compound is isopropanol.

5. The process of claim 1 wherein the oxygen-containing essentiallynon-reacting water-miscible organic compound is a water-miscible ketone.

6. The process of claim 1 wherein the oxygen-containing essentiallynon-reacting water-miscible organic compound is acetone.

7. The process of claim 1 wherein the total refluxing temperature is inthe range of from about 50 C. to about 100 C.

8. The process of claim 1 wherein the linearly unsaturated hydrocarbonis a polymer.

9. The process of claim 1 wherein the linearly unsaturated hydrocarbonis reacted with from 0.3 to 2.0 moles of sulfur chloride per mole oflinearly unsaturated hydrocarbon.

1-0. The process of claim 1 wherein the sulfur chloride is sulfurmono-chloride.

11. The process of claim 1 wherein the sulfur chloride treatment iscarried out in the presence of water.

12. The process of claim 1 wherein the sulfur chloride treatment iscarried out in the presence of a phosphorus sulfide.

13. A method for producing high sulfur-containing compositions of lightcolor and high color stability which comprises the steps of reacting alinearly unsaturated hydrocarbon with sulfur chloride in the presence of1 to 50 volume percent water, and refluxing the resulting reactionproduct in the presence of substantial portions of a mixture ofwater-miscible alcohol and water wherein the water and oxygen-containingcompound in said mixture are each present in substantial percents at thetotal refluxing temperature for at least minutes.

14. A method for producing high sulfur and phosphorus-containingcompositions of light color and high color stability which comprises thesteps of adding to a linearly unsaturated hydrocarbon from about .0025to about 0.2 mole of phosphorus sulfide per mole of linearly unsaturatedhydrocarbon, treating said linearly unsaturated hydrocarbon andphosphorus sulfide with sulfur chloride, and refluxing the reactionmixture in the presence of substantial portions of a mixture ofwatermiscible alcohol and water wherein the water and alcohol in saidmixture are each present in substantial percents at the total refluxingtemperature for at least 10 minutes.

15. The process of claim 14 in which the phosphorus sulfide is P 8 16. Amethod for producing high sulfur and phosphorus containing compositionsof light color and high color stability which comprises the steps ofadding to a linearly unsaturated hydrocarbon from about .0025 to about0.2 mole of phosphorus sulfide per mole of linearly unsaturatedhydrocarbon, incrementally treating said linearly unsaturatedhydrocarbon and phosphorus sulfide with 0.3 to 2.0 moles of sulfurchloride per mole of linearly unsaturated hydrocarbon in the presence of1 to 50 volume percent Water so as not to exceed the boiling point ofthe reaction mixture, and refluxing the reaction mixture in the presenceof substantial portions of a water-miscible alcohol and water whereinthe water and alcohol in said mixture are each present in substantialpercents at the total refluxing temperature for at least 10 minutes.

17. A process for sulfochlorinating linearly unsaturated hydrocarbonswhich comprises the steps of incrementally treating a linearlyunsaturated hydrocarbon with from about 0.3 to about 2.0 moles. ofsulfur chloride per mole of linearly unsaturated hydrocarbon,maintaining the reaction at a temperature not exceeding about C., addingsubstantial portions of a first mixture of a water-miscible alcohol andwater to the reactants, refluxing the mixture at the total refluxingtemperature, separating a water layer from the reactants, addingsubstantial portions of a second mixture of a water-miscible alcohol andwater to the reactants, repeating the refluxing at the total refluxingtemperature, separating a water layer from the reactants, and removingunreacted linearly unsaturated hydrocarbons from the reactants, whereinthe water and alcohol in said first and second mixtures are each presentin substantial percents.

18. The product formed by the process of claim 1.

19. The product formed by the process of claim 14.

20. The product formed by the process of claim 16.

21. A method for producing high sulfur-containing compositions of lightcolor and high color stability, which method comprises the steps ofreacting a linearly unsaturated hydrocarbon with a sulfur chloride andrefluxing the resulting sulfochlorinated hydrocarbon in the presence ofabout 500 milliliters of a mixture of water and an oxygen-containingessentially non-reacting water-miscible organic compound boiling in therange of 50 to C. per 1000 grams of said linearly unsaturatedhydrocarbon, said refluxing being at the reflux temperature of saidmixture.

References Cited in the file of this patent UNITED STATES PATENTS2,708,199 Eby May 10, 1955 2,727,030 Beretvas Dec. 13, 1955 2,853,480Lindert Sept. 23, 1958

1. IN A PROCESS FOR THE SULFOCHLORINATION OF LINEARLY UNSATURATEDHYDROCARBONS THE STEPS COMPRISING REACTING A LINEARLY UNSATURATEDHYDROCARBON WITH A SULFUR CHLORIDE AND REFLUXING THE RESULTINGSULFOCHLORINATED HYDROCARBON IN THE PRESENCE OF SUBSTANTIAL PORTIONS OFA MIXTURE OF WATER AND AN OXYGEN-CONTAINING ESSENTIALLY NON-REACTINGWATER-MISCIBLE ORGANIC COMPOUND WHEREIN THE WATER AND OXYGEN-CONTAININGCOMPOUND IN SAID MIXTURE ARE EACH PRESENT IN SUBSTANTIAL PERCENTS AT THETOTAL REFLUXING TEMPERATURE, SAID OXYGEN-CONTAINING COMPOUND BOILINGBELOW ABOUT 100*C.